Patent GB-297855-A (GB)
Title: Manufacture of new intermediate compounds and of azo dyes therefrom
IPC: C07C65/01
Filed: 1927-05-27
Abstract: 297,855. British Dyestuffs Corporation, Ltd., and Mendoza, M. May 27, 1927. Nitro- and amino-diarylsulphones.-5-Substituted and the 5 : 6-benzo-substituted aminodiarylsulphones of the type in which Ar represents an aromatic residue carrying at least one amino group, are obtained by reduction of the products of condensation of the corresponding sulphinic acids with an aromatic nitro compound carrying labile halogen. Specified nitro compounds are 1-chloro-2-nitrobenzene and its 4-sulphonic acid, 1-chloro-4-nitrobenzene and its 2-sulphonic acid, 1-chlor-2 : 4- dinitrobenzene, 1-chloro-2 : 4-dinitronaphthalene, 4 - chloro - 3 - nitrobenzaldehyde, 4-chloro-3-nitrobenzoic acid and its nitrile, and 2-chloro-5-nitrobenzoic acid and its nitrile. In examples (1) 3- sulphino-5-methyl (or chloro) salicylic acid or 1- sulphino-2 : 3-oxynaphthoic acid is condensed with 1-chloro-2-nitrobenzene-4-sulphanic acid or 1- chloro-4-nitrobenzene-2-sulphonic acid, and the nitrosulphone is reduced, without isolation if desired, e.g. by iron filings and acid or by stannous chloride; (2) the same sulphino derivatives are condensed with 2 : 4-dinitrochlorobenzene or 2 : 6- nitrochlorobenzene-4-sulphonic acid and the nitrosnlphones are reduced. Sulphinic acids-3-Sulphino-5-methyl (or 5- chlom) salicylic acid and 1-sulphino-2 : 3-oxynaphthoic acid are obtained by reduction, e.g. with zinc dust, of the sulphonic chlorides produced by treatment of p-cresotinic (or 5-chloro-) salicylic acid and 2 : 3-oxynaphthoic acid respectively with chlorosulphonic acid. Azo dyes.-The above aminodiarylsulphones are used as components in the manufacture of azo dyes in which the separation of a reactive group from a chelate group by the sulphone bridge enables chroming to be effected without change of shade. The monoaminosulphones may be diazotized and coupled with the usual components, and the diaminosulphones may be used as second components, or may be monacylated and used as first, components, or may be treated' with nitrous acid to produce dyes of the Bismarck brown type, or may in some cases be used as tetrazo components. In examples the following dyestuffs are specified:-(1) 5-methyl (or chloro)- 2-oxy - 3 - carboxy-2<1>-amino-4<1>-sulphodiphenyl sulphone or 2 - oxy-3-carboxynaphthyl-2<1>-amino-4<1>- sulphophenyl sulphone # #-naphthol, 1-(2<1> : 5<1>-dichlor-4<1>-sulpho)phenyl-3-methyl-5-pyrazolone, 1-(4<1>-sulpho)phenyl-3-methyl-5-pyrazolone, 2.: 3- oxynaphthoic anilide, 2-naphthol-3 : 6-disulphonic acid, 1 : 5-naphtholsulphonic acid, ethyl-a-naphthylamine, or 2 : 8 : 6 acid (acid coupled); (2) 5- methyl - 2 - oxy - 3 - carboxy-2<1>-amino-4<1>-sulphodiphenyl sulphone # (acid) 2 : 8 : 6 acid - pnitraniline; (3) 5-methyl - 2 - oxy-3-carboxy-2<1>- amino-4<1>-sulphodiphenyl sulphone # m-aminop-cresol methyl ether # (alkaline) phenyl-2- : 5: 7-acid, #-naphthol, salicylic acid, or chromotropic acid; (4) benzidine # salicylic acid (1 mol.) and the dyestuff (1 mol.) from diazotized 5 - chloro - 2 - oxy-3-carhoxy-2<1>-amino-4<1>-sulphodiphenyl sulphone and H-acid : (5) 5-methyl (or chloro) - 2-oxy-3-carboxy-2<1>: 6<1>-diamino-4<1>-sulphodiphenyl sulphone or 2-oxy-3-carboxynaphthyl-2<1> : 6' - diamino - 4' - sulphophenyl sulphone # #-naphthol or acetyl-H-acid (2 mols.); (6) 1 : 4- naphthylamine sulphonic acid or 4-nitraniline-2- sulphonic acid # 5-methyl (or chloro)-2-oxy-3- carboxy-2<1> : 4<1>-diaminodiphenyl sulphone or 2-oxy- 3-carboxynaphthyl-2<1> :4<1>-diaminophenyl sulphone; (7) benzidine-2 : 2'-disulphonic acid # 2 mols. of one of the diaminosulphones in (6); (8) aniline # 1 : 7-naphthylaminesulphonic acid # one of the diaminosulphones in (6) ; (9) the N-monoacetyl derivative of 5-methyl (or chloro)- 2-oxy-3-carboxy-2<1> : 4<1>-diamino (or 2<1> : 6' - diamino-4<1>-sulpho) diphenyl sulphone or 2-oxy-3- carboxynaphthyl - 2' : 4'-diaminophenyl sulphone # (acid) 2: 8: 6-acid, 1 5-naphtholsulphonic acid, or 1-(2<1> : 5<1>-dichloro - 4<1> - sulpho)phenyl-3- methyl-5-pyrazolone. Specifications 245,865 and 262,243 are referred to.